CN110026174A - High thermal stability CeO2-ZrO2Based oxygen storage material and preparation method thereof - Google Patents
High thermal stability CeO2-ZrO2Based oxygen storage material and preparation method thereof Download PDFInfo
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- CN110026174A CN110026174A CN201811519624.9A CN201811519624A CN110026174A CN 110026174 A CN110026174 A CN 110026174A CN 201811519624 A CN201811519624 A CN 201811519624A CN 110026174 A CN110026174 A CN 110026174A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The present invention provides high thermal stability CeO2‑ZrO2Based oxygen storage material and preparation method thereof, central scope are: for determining CeO2‑ZrO2The feed ratio of based oxygen storage material after precursor salt solution is pressed different Ce/Zr scores into several pieces, then uses coprecipitation to be reacted with lye.CeO prepared by this method2‑ZrO2Based oxygen storage material has both high thermal stability, high reproducibility and high-specific surface area.
Description
Technical field
The invention belongs to hydrogen-storing material field, in particular to a kind of CeO2-ZrO2Based oxygen storage material.
Background technique
Motor-vehicle tail-gas is one of main source of atmosphere pollution, major pollutants hydrocarbon (HC) therein,
Oxynitrides (NOx), carbon monoxide (CO) and particulate matter (PM) not only cause serious environmental pollution, be also carcinogen,
Endanger the health of the mankind.Three-way catalyst (TWCs) can under the conditions of chemically correct fuel simultaneously will be in motor-vehicle tail-gas
(HC), oxynitrides (NOx), carbon monoxide (CO) be converted to harmless H2O, CO2And N2。
CeO2-ZrO2Based oxygen storage material is suitable for lean/rich combustion item due to the performance with excellent storage oxygen and release oxygen
Catalysis reaction under part.Therefore with CeO2-ZrO2Three-way catalyst as storage oxygen release component is widely used in wider air-fuel ratio item
Real vehicle tail gas clean-up under part.With the emission regulation being increasingly stringenter, there is an urgent need to further increase purifying vehicle exhaust three
Imitate the thermal stability of catalyst (TWCs).And CeO2-ZrO2Solid solution, as crucial carrier material, removes in the formula of TWCs
To its redox property, other than texture property requires, high high-temp stability is even more important in actual application.It is excellent
Different thermal stability can reduce the collapsing of cellular structure in use and lead to the embedding of active component, improve catalyst
Endurance quality.
It is mainly assisted at present by doping auxiliary agent ion, using surfactant and optimizes preparation method to improve CeO2-
ZrO2The thermostabilization of solid solution.Wherein, optimization preparation method may be implemented in do not introduce remaining substance under the premise of realize thermostabilization
Raising, it is cost-saved in industrial application.Therefore, how research optimizes and accurately controls CeO2-ZrO2Preparation process parameter
It is of great significance for improving its thermal stability.
Summary of the invention
The purpose of the present invention is to provide a kind of CeO2-ZrO2The preparation method of based oxygen storage material, prepared by this method
CeO2-ZrO2Based oxygen storage material has both high thermal stability, high reproducibility and high-specific surface area.
The CeO of high heat stability of the present invention, high reducing property and high-specific surface area2-ZrO2Based oxygen storage material can be
CeO2-ZrO2Material is also possible to the stable CeO of at least one doped chemical2-ZrO2Hydrogen-storing material, doped chemical can be alkali
Earth metal, Al element, at least one of the element that transition metal, Y element or atomic number are 57~71.In hydrogen-storing material,
The content of cerium oxide is 10%~80wt%.
High thermal stability CeO provided by the invention2-ZrO2The preparation method of based oxygen storage material, central scope are: for true
Fixed CeO2-ZrO2The feed ratio of based oxygen storage material, after precursor salt solution is pressed different Ce/Zr scores into several pieces, then
It is reacted using coprecipitation with lye, the specific process steps are as follows:
(1) according to the CeO that need to be prepared2-ZrO2The chemical composition of based oxygen storage material, according to CeO2、ZrO2Ratio weigh pair
Each presoma is dissolved in deionized water and is uniformly mixed, is configured to precursor salt solution by the presoma answered；Or, according to needing to make
Standby CeO2-ZrO2After determining Ce, Zr total amount, according to different Ce/Zr ratios, presoma is made into for the chemical composition of based oxygen storage material
Several pieces have the precursor salt solution of different Ce/Zr ratios；
(2) using lye as precipitating reagent, lye and precursor salt solution are titrated simultaneously under agitation, in the process control volume
Be pH be 8.0~10；When precursor solution is the precursor salt solution that several pieces have different Ce/Zr ratios, not by several pieces
Precursor salt solution with Ce/Zr ratio is titrated (synchronous titration) with aqueous slkali simultaneously, or is titrated by several times with lye；
Titration terminates to obtain suspension；
(3) gained suspension is aged 2~for 24 hours, or after being filtered by gained suspension, wash, size mixing again it is old again
Change 2~for 24 hours, ageing carries out under air atmosphere or inert atmosphere, under 60~100 DEG C and normal pressure or in 60~100 DEG C of high pressures
Pressurized conditions carry out in reaction kettle；
(4) suspension after ageing filtered, obtain solid after washing, by solid in 400-600 DEG C of roasting 3-6h, obtained
Fresh CeO2-ZrO2Based oxygen storage material, roasting process can be carried out in air atmosphere, can also be carried out in atmosphere of inert gases；
It is warming up to 1000 DEG C of roasting 3-6h again and obtains the CeO of aging2-ZrO2Based oxygen storage material；
Further, control system pH is 8.5~9.3 in step (2) titration process.
Further, step (2) titration process is controlled at 40~80 DEG C.
Further, step (1) presoma is nitrate, carbonate, acetate etc., and wherein the presoma of cerium is best
For ammonium ceric nitrate, and Ce (III) is oxidized to Ce (IV) preferably with oxidant.Oxidant is preferably hydrogen peroxide.
Further, step (2) lye is the corresponding hydroxide solution of alkali or alkaline earth metal, ammonium hydroxide, carbon
Sour ammonia solution, ammonium bicarbonate soln, urea liquid etc., and two or three of mixed solution in preferably above-mentioned lye.
Further, the surfactant is selected from anionic surfactant, cationic surfactant and nonionic
Surfactant.Preferably C atomicity is one of 8~20 fatty acid, fatty alcohol, fatty amine or a variety of.
Further, before step (4) is filtered, surfactant is added into the suspension after ageing, or in step
(4) it sizes mixing again after obtaining solid, then adds surfactant, or directly obtain adding surface-active in solid in step (4)
Agent；Then it is filtered again, successively washs filter cake with water, ammonium hydroxide, salting liquid and obtain solid；Preferably, surfactant adds
Dosage is 15wt%-60wt%.
Further, the additive amount of step (4) surfactant is preferably 20wt%-55wt%.
Further, 2-2.5h is reacted under 60 DEG C of water bath conditions after surfactant addition.
Further, step (4) Aging Temperature is preferably controlled in 100 DEG C, and the time is preferably 4~12h.
Further, step (4) heating rate can be controlled in 5~10 DEG C/min.
The present invention provides the CeO of above method preparation2-ZrO2Based oxygen storage material, prepared CeO2-ZrO2Base stores up oxygen
Material has both high thermal stability, high reproducibility and high-specific surface area.
Compared with prior art, the invention has the following advantages:
1. the method for the invention passes through fixed CeO2-ZrO2The feed ratio of based oxygen storage material, by precursor salt solution by not
With Ce/Zr score at several pieces after, then reacted with lye using coprecipitation, be prepared have both high thermal stability,
The CeO of high reducing property and high-ratio surface2-ZrO2Based oxygen storage material, after 1000 DEG C/4h aging, reduction peak is minimum < and 500 DEG C,
Specific surface area is at least 40m2/g。
2, the method for the invention is remarkably improved CeO under the premise of not introducing other additives2-ZrO2Base stores up oxygen material
The thermal stability of material, prospects for commercial application are higher.
Detailed description of the invention
CeO in Fig. 1 embodiment 12-ZrO2-Y2O3-La2O3The H of material2(figure a is fresh material to-TPR figure, and figure b is aging
Material)；
CeO in Fig. 2 embodiment 22-ZrO2The H of material2- TPR figure (figure a is fresh material, and figure b is aging material).
Specific embodiment
Below by specific embodiment to high thermal stability CeO of the present invention2-ZrO2The preparation side of based oxygen storage material
Method is described further.
Embodiment 1
Prepare CeO2-ZrO2-Y2O3-La2O3Hydrogen-storing material:
(1) fixed CeO2-ZrO2-Y2O3-La2O3Group become 45wt%CeO2: 45wt%ZrO2: 5wt%Y2O3: 5wt%
La2O3, the corresponding precursor salt of cerium, lanthanum, yttrium is nitrate, and the precursor salt of zirconium is zirconyl carbonate, and zirconyl carbonate is using certain
The concentrated nitric acid of amount is dissolved.Presoma is configured to two parts of precursor salt solution by different Ce/Zr ratios, concrete composition is shown in Table
1；
(2) two parts of salting liquids are co-precipitated simultaneously with lye as precipitating reagent using the mixed solution of ammonium hydroxide and ammonium carbonate,
The pH of system in titration process is controlled 8.8~9.0, obtains suspension；
(3) by 98 DEG C of ageing 6h of gained suspension；
(4) it is directly added into the lauric acid of hydrogen-storing material 40wt% into the suspension after ageing, stirs evenly, then carries out
It filters, carries out washing filter cake with water, ammonium hydroxide, salting liquid, obtain intermediate；
(5) gained intermediate is obtained into fresh material in 600 DEG C of roasting 3h, then is warming up to 1000 DEG C of roasting 4h and obtains aging
Material.
Comparative example 1
Prepare the CeO of composition same as Example 12-ZrO2-Y2O3-La2O3Hydrogen-storing material, except all presomas will be matched
Salt is dissolved into a precursor salt solution together and lye titrates outside simultaneously, is prepared using method same as Example 1
Compare CeO2-ZrO2-Y2O3-La2O3Material.Its reducing property and texture property are shown in Fig. 1 and table 2 respectively.CeO2-ZrO2Base stores up oxygen
The test of material reducing property is in 5%H2/N2Atmosphere under obtained from room temperature temperature programmed reduction to 900 DEG C.Texture property is logical
What automatic absorbing instrument (Autosorb SI) test of Guo Kang tower company obtained.Crystallite dimension is using XRD diffraction maximum, by thanking
Happy formula obtains.By comparing specific surface area, the crystallite dimension of fresh material and aging material, show that aging material is relatively new fresh
The specific surface area loss late of material and the growth rate of crystallite dimension, the stability of material is indicated with this.Concrete outcome is shown in Table 2.
Table 1
Table 2
As can be seen from Table 1: using the CeO for improving coprecipitation preparation2-ZrO2-Y2O3-La2O3Material is old at 1000 DEG C
Higher specific surface area (> 40m can be maintained after changing 4h2/ g) and lesser grain growth rate.This explanation is improved using the present invention
Coprecipitation can significantly improve CeO2-ZrO2-Y2O3-La2O3The thermal stability of material.
As seen from Figure 1: using the CeO for improving coprecipitation preparation2-ZrO2-Y2O3-La2O3In 1000 DEG C of aging 4h
Afterwards, most strong reduction peak temperature is at 480 DEG C, compared with CeO prepared by comparative example 12-ZrO2-Y2O3-La2O3Most strong reduction peak temperature drop
Low 108 DEG C.This also illustrates the CeO using the method for the present invention preparation2-ZrO2-Y2O3-La2O3Material also has both going back for high heat stability
Originality energy.
Embodiment 2
Prepare CeO2-ZrO2Storage material:
(1) fixed CeO2-ZrO2Group become Ce:Zr=1:1 (mol/mol), by presoma needed for ingredient according to Ce/Zr
=1/3 and Ce/Zr=3/1 is configured to two parts of salting liquids；Cerium precursor is nitrate, and the precursor salt of zirconium is zirconyl carbonate, carbon
Sour oxygen zirconium is dissolved using a certain amount of concentrated nitric acid；
(2) two parts of salting liquids are co-precipitated simultaneously with lye as precipitating reagent using the mixed solution of ammonium hydroxide and ammonium carbonate,
The pH of system in titration process is controlled in 8.8-9.0, obtains suspension；
(3) suspension after precipitating is aged 6h at 98 DEG C；
(4) suspension after ageing filtered, roast 3h at 600 DEG C respectively after washing, then be warming up to 1000 DEG C of roastings 4
h。
Comparative example 2
Prepare the CeO of composition same as Example 12-ZrO2-Y2O3-La2O3Hydrogen-storing material, required all precursor salts one
It rises and is dissolved into a precursor salt solution and lye titrate outside simultaneously, comparison is prepared using method same as Example 2
CeO2-ZrO2Material.
Comparative example 3
The CeO of Ce/Zr=1/3 is prepared separately using preparation method same as Example 22-ZrO2Material.
Comparative example 4
The CeO of Ce/Zr=3/1 is prepared separately using preparation method same as Example 22-ZrO2Material.
The performance of the material of preparation is investigated using test same as Example 1 and calculation method, concrete outcome is shown in Table 3 Hes
Fig. 2.
Table 3
As can be seen from Table 3: in the case where being not added with any auxiliary agent, still can be improved using coprecipitation is improved
CeO2-ZrO2The thermal stability of material.For comparative example 2, using the CeO of modified co-precipitation preparation of the invention2-ZrO2?
Higher specific surface area and lesser crystallite dimension and preferable reducing property (Fig. 2) can be maintained after 1000 DEG C of aging 4h.
Embodiment 3
Prepare CeO2-ZrO2-La2O3Hydrogen-storing material.
Fixed CeO2-ZrO2-La2O3Feed ratio group become 45wt%CeO2: 45wt%ZrO2: 10wt%La2O3.Forerunner
Body salting liquid is divided into two parts, and composition is respectively as follows: CeO2:ZrO2:Y2O3:La2O3=25wt%:65wt%:5wt% and CeO2:
ZrO2:Y2O3:La2O3=65wt%:25wt%:5wt%.
Remaining preparation method is same as Example 1.
Comparative example 5
All precursor salts needed for by ingredient are dissolved into a precursor salt solution and together in addition to lye titrate simultaneously, adopt
Comparison CeO is prepared with method same as Example 32-ZrO2-La2O3Material.
Comparative example 6
By 3 feed ratio of embodiment, precursor salt solution is divided into two parts, at being respectively as follows: CeO2:ZrO2:Y2O3:La2O3=
25 wt%:65wt%:5wt% and CeO2:ZrO2:Y2O3:La2O3=65wt%:25wt%:5wt%.It is co-precipitated titration process
In, group is first become into CeO2:ZrO2:Y2O3:La2O3The salting liquid of=25wt%:65wt%:5wt% mixes again after mixing with lye
Close remaining composition.Remaining preparation process is same as Example 3.
Comparative example 7
It is identical as the preparation method of comparative example 6, only change the titration sequence of salting liquid: group first being become into CeO2:ZrO2:
Y2O3: La2O3The salting liquid of=65wt%:25wt%:5wt% remixes remaining composition after mixing with lye.
Test and calculation method in the present embodiment is same as Example 1, and concrete outcome is shown in Table 4.
Table 4
As can be seen from Table 4: for comparative example 5, being either co-precipitated (embodiment 3) simultaneously or using fractional precipitation
(comparative example 6-7), using the CeO of modified co-precipitation preparation of the invention2-ZrO2It can be maintained after 1000 DEG C of aging 4h higher
Specific surface area and lesser grain growth rate.Prove that this explanation can be significantly improved using improved coprecipitation again
CeO2-ZrO2The thermal stability of based oxygen storage material.
Claims (10)
1. high thermal stability CeO2-ZrO2The preparation method of based oxygen storage material, which is characterized in that including processing step in detail below
It is as follows:
(1) according to the CeO that need to be prepared2-ZrO2The chemical composition of based oxygen storage material, according to CeO2、ZrO2Ratio weigh it is corresponding
Each presoma is dissolved in deionized water and is uniformly mixed, is configured to precursor salt solution by presoma；Or, according to that need to prepare
CeO2-ZrO2The chemical composition of based oxygen storage material after determining Ce, Zr total amount, according to different Ce/Zr ratios, presoma is made into several
Part has the precursor salt solution of different Ce/Zr ratios；
(2) using lye as precipitating reagent, lye and precursor salt solution are titrated simultaneously under agitation, in the process control system pH
It is 8.0~10；When precursor solution is the precursor salt solution that several pieces have different Ce/Zr ratios, by several pieces difference Ce/
The precursor salt solution of Zr ratio is titrated (synchronous titration) with aqueous slkali simultaneously, or is titrated by several times with lye；Titration knot
Beam obtains suspension；
(3) gained suspension is aged 2~for 24 hours, or gained suspension filtered, wash, size mixing again after be aged 2 again~
For 24 hours, ageing carries out under air atmosphere or inert atmosphere, under 60~100 DEG C and normal pressure or in 60~100 DEG C of autoclaves
Middle pressurized conditions carry out；
(4) suspension after ageing filtered, obtain solid after washing, by solid in 400-600 DEG C of roasting 3-6h, obtained fresh
CeO2-ZrO2Based oxygen storage material, roasting process can be carried out in air atmosphere, can also be carried out in atmosphere of inert gases；It rises again
Temperature obtains the CeO of aging to 1000 DEG C of roasting 3-6h2-ZrO2Based oxygen storage material.
2. preparation method according to claim 1, which is characterized in that in step (2) titration process control system pH be 8.5~
9.3, controlled at 40~80 DEG C.
3. preparation method according to claim 1, which is characterized in that step (1) presoma be nitrate, carbonate,
One of acetate.
4. preparation method according to claim 1, which is characterized in that step (2) lye is alkali or alkaline earth metal
At least one of corresponding hydroxide solution, ammonium hydroxide, carbonic acid ammonia solution, ammonium bicarbonate soln, urea liquid.
5. preparation method according to claim 1, which is characterized in that the surfactant is selected from anion surface active
Agent, cationic surfactant and nonionic surfactant.
6. preparation method according to claim 1, which is characterized in that before step (4) is filtered, to the suspension after ageing
Middle addition surfactant, or size mixing again after step (4) obtains solid, then add surfactant, or directly in step
(4) it obtains adding surfactant in solid；Then it is filtered again, successively washs filter cake with water, ammonium hydroxide, salting liquid and consolidated
Body；The additive amount of surfactant is 15wt%-60wt%.
7. preparation method according to claim 6, which is characterized in that the additive amount of step (4) surfactant is preferably
20wt%-55wt%.
8. preparation method according to claim 6, which is characterized in that anti-under 60 DEG C of water bath conditions after surfactant addition
Answer 2-2.5h.
9. preparation method according to claim 1, which is characterized in that step (4) Aging Temperature is preferably controlled in 100 DEG C, when
Between preferably 4~12h.
10. the high thermal stability CeO that in claim 1-9 prepared by any claim the method2-ZrO2Based oxygen storage material.
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